Diesel fuel

Abstract: A low sulfur diesel fuel which contains a di- and/or tri-C₁₋₁₀ alkyl ether of glycerol in amount sufficient to reduce particulate matter emissions. Methyl soyate and/or a cetane improver may also be included. Also provided is a novel mixture comprising a predominant amount of 1,3-di-t-alkyl glycerol and also comprising 1,2-di-t-alkyl glycerol and 1,2,3-tri-t-alkyl glycerol.

Description: Background of the Invention Field of the Invention The present invention relates to an improved diesel fuel which has reduced particulate matter emission characteristics and which contains an effective amount of a dialkyl ether and/or trialkyl ether derivative of glycerol and most preferably the glycerol di-t-butyl ether product mixture prepared by glycerol etherification with isobutylene or t-butanol. Description of the Prior Art Diesel fuels are known which contain a synergistic cetane improving additive combination of a peroxidic component and an aliphatic polyether of the formula R(-O-X) n O-R 1 where R and R 1 are alkyl groups, X is an alkylene group and n is an integer. See U.S. Patent 2,655,440 and divisional U.S. Patent 2,763,537. European Application 80-100827.7 describes the use of various propylene glycol mono- and di-ethers as a component of diesel fuels. The compositions described in this reference involve a multicomponent formulation which includes poly-ethers, acetals, lower alkanols, water and only up to 85 volume % diesel fuel hydrocarbons. U.K. 1,246,853 describes the addition of dialkyl ethers of propylene glycol as smoke suppressants in diesel fuel. U.S. Patent 4,753,661 describes a fuel such as diesel fuel containing a conditioner which comprises a polar oxygenated hydrocarbon, a compatibilizing agent which is an alcohol, aromatics, and a hydrophilic separant which may be a glycol monoether. Japanese Published Application 59-232176 describes the use of the di-ethers of various polyoxyalkalene compounds as diesel fuel additives. The addition of glycol ethers and metallic smoke suppressants have been found to reduce the smoke and soot emissions. These metallic smoke suppressants are typically metal salts of alkanoic acids. Both the health and environmental risks of these salts, especially those of barium, are of concern. See U.S. 3,594,138, U.S. 3,594,140, U.S. 3,615,292 and U.S. 3,577,228. EP-A-0 077 027 describes the use of ethers to reduce soot. However, a number of these ethers are unable to be used commercially in the U.S. because the resulting fuel does not meet the flash point specification of 126°F. This application also teaches that glycol ethers are not highly effective at reducing exhaust emissions. Based on these teachings, our invention would be unexpected. Japanese Patent Application 59-232176 teaches that glycol ethers of the formula R 1 -O-(CHR 2 -CH 2 -O-) n R 3 where n is less than five have the effect of reducing particulate, CO and HC emissions which effect is weak. This is in direct contrast to our invention. Winsor and Bennethum (SAE 912325) describe the use of the ether diglyme to reduce particulate emissions. In addition to being costly to produce, diglyme is highly toxic and has been associated with increased rates of miscarriages. Glycol ethers based on the higher alkylene oxides, especially propylene and the butylenes, are far less toxic than those based on ethylene oxide. Glycol ethers based on ethylene oxide also have unfavorable water partition coefficients. The water partition coefficient for diglyme is greater than 17. Thus virtually eliminating it for any commercial use as a diesel fuel additive. The addition of dialkyl carbonates and dialkyl dicarbonates, particularly dimethyl carbonate, to diesel fuel has been described to reduce exhaust emissions from compression ignition engines. See U.S. Patents: 2,311,386, 4,891,049, 5,004,480 and 4,904,279. The high volatility of the lower alkyl carbonates prevents their addition in substantial amounts to typical D-2 diesel fuel. While some dicarbonates have lower volatilities, their poor hydrolytic stability precludes their commercial use. The Clean Air Act Amendments of 1990 have established certain emission standards for heavy duty diesel engines, in particular with regard to nitrogen oxide and particulate matter emissions. The contribution of diesel fuel sulfur content to exhaust particulates has been well established, and has led to an EPA regulation which will require highway diesel fuels to contain no more than 0.05 wt.% sulfur. In 1991, particulate matter emissions were required to drop from 0.60 to 0.25 grams/BHP-hr., and in 1994 the emission limit is 0.10. Similarly, nitrogen oxide will decrease from 6.0 to 5.0 in 1994 and from 5.0 to 4.0 grams/BHP-hr. in 1998. The California Air Resources Board (CARB) has issued regulations that are viewed as more difficult to meet than the EPA targets. To qualify as a diesel fuel in California, emissions must be no greater than the CARB reference fuel which contains 0.05 wt.% maximum sulfur, 10% maximum aromatics and a minimum cetane number of 48. Many strategies are being used by the industry to reduce emissions. Improved heavy duty diesel engine designs including higher injection pressures, turbocharging, air intercooling, retarded injection timing through electronic tuning control, exhaust gas recycle and exhaust aftertreatment devices all lower emissions. For this advanced technology to work, a high quality, low emissions diesel fuel is required in addition to the use of various fuel additive improvements including cetane improver use, diesel fuel detergents to keep fuel injectors clean and improved low ash engine oils. A combination of these strategies will be utilized to meet new clean air standards. The key issue is to find the most effective combination of technologies which offer the best cost/performance. Fuel regulations, especially those promulgated in California, will require costly changes in diesel fuel composition. Desulfurization to achieve the 0.05 wt.% sulfur target is easily accomplished through mild hydrogenation. However, refiners must use deep hydrogenation to decrease aromatic content from the current 20 - 50% aromatic level down to 10%. Several refiners have elected to exit the California diesel fuel market rather than making the high capital investment required for deep hydrogenation. At least one refiner was able to qualify a diesel fuel for California by lowering the aromatics to 19% and increasing the cetane number from 43 for a typical fuel up to around 60 using an alkyl nitrate cetane improver. The present invention relates to the use of ether derivatives of glycerol which, when incorporated in standard 30-40% aromatic containing diesel fuel, provides reduced emissions of particulate matter, hydrocarbons, carbon monoxide and unregulated aldehyde emissions. For 1994, the engine manufacturer strategy to reduce emissions in order to meet the emission regulations involves using electronic tuning to reduce particulates. In this strategy, nitrogen oxide, hydrocarbons, and carbon monoxide emissions are within EPA requirements. However, for 1998, nitrogen oxide emissions need to be further reduced. If an oxygenated fuel can lower particulate matter emissions another 10-20%, this will provide additional tuning flexibility for nitrogen oxide. The strategy would be to lower particulates to meet the 0.1 gram/BHP-hr. target using a combination of oxygenate additive, cetane additive, and tuning. This widens the window for nitrogen oxide tuning which needs to be reduced from 5.0 to 4.0 grams/BHP-hr. Particulate reductions will also provide an opportunity to further lower nitrogen oxide using exhaust gas recycle. At high particulate matter levels, the particulates block and foul the exhaust gas recycle lines and orifices, and contaminate engine oil. Lower particulates via the use of ether derivatives of glycerol could allow greater use of this new technology. Brief Description of the Invention In accordance with the invention, reduced emissions of particulate matter are achieved with a fuel composition comprised of hydrocarbons and/or vegetable oil derivatives boiling in the diesel fuel range and containing up to 500 ppm sulfur, and a particulate emission reducing amount of an additive comprising at least one glycerol ether having the formula wherein R 1 , and R 2 and R 3 are each hydrogen or a C 1 -C 10 alkyl group with the proviso that at least two of R 1 , R 2 or R 3 are C 1 -C 10 alkyl groups. Preferably, R 1 and R 3 are the same alkyl group, such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, amyl, t-amyl, hexyl, hextyl, octyl, nonyl, decyl and the like. Most preferably, R 1 and R 3 are the same C 4 -C 5 tertiary alkyl group. Mixtures can be employed including mixtures of additives with different alkyl groups, mixtures of 1,2 diether, 1,3 diether and 1,2,3 triether are preferred. Some other preferred embodiments are found in Claims 2 to 12 of the accompanying claims. Especially suitable for use according to the invention is the mixture of 1,2 di-t-alkyl, 1,3-di-t-alkyl and 1,2,3-tri-t-alkyl glycerol ethers prepared by glycerol etherification with an isoalkene such as isobutylene or t-amylene or with a t-alkyl alcohol such as t-butanol or t-amyl alcohol. The hydrocarbon based diesel fuels utilized in the practice of this invention are comprised in general of mixtures of hydrocarbons which fall within the diesel fuel boiling range, typically 160° to 370°C. The fuels are often referred to as middle distillate fuels since they comprise the fractions which distill after gasoline. The diesel fuels of the invention have a low sulfur content, i.e. not more than 500 ppm by weight, preferably not more than 100 ppm and preferably not more than 60 ppm sulfur by weight. Aromatic content is in the range of 0-50% by volume, preferably 20-35% by volume. The glycerol ether component employed in the invention has the formula where R 1 , R 2 and R 3 are each hydrogen or a C 1 -C 10 alkyl group with the proviso that at least two of R 1 , R 2 or R 3 are the C 1 -C 10 alkyl group. Preferably R 1 and R 3 are the same alkyl group; most preferably, R 1 and R 3 are the same C 4 -C 5 tertiary alkyl group. Especially preferred additives are 1,3 di-t-butyl glycerol or mixtures of 1,3 di-t-butyl glycerol with 1,2 di-t-butyl glycerol and 1,2,3 tri-t-butyl glycerol. These additives have good solubilities in diesel fuel hydrocarbons, have superior water partition coefficient characteristics and are effective in reducing particulate matter emissions. The diesel fuel formulations of the present invention consist essentially by volume of at least 85% diesel fuel hydrocarbons and 0.1 to up to 15% of the glycerol ether, preferably about 0.2 to 10% of the glycerol ether. Conventional additives and blending agents for diesel fuel may be present in the fuel compositions of this invention in addition to the above components. For example, the fuels of this invention may contain conventional quantities of such conventional additives as cetane improvers, friction modifiers, detergents, antioxidants and heat stabilizers, for example. Especially preferred diesel fuel formations of the invention comprise diesel fuel hydrocarbons and monoalkyl ether as above described together with peroxidic or nitrate cetane improvers such as ditertiary butyl peroxide, amyl nitrate and ethyl hexyl nitrate for example. The addition of the glycerol ether additives in accordance with the invention results in a slight increase in NO x emissions; however, the use of sufficient known cetane improvers to increase the fuel cetane value by 5-10 units reduces the NO x emissions well below the level of the base reference fuel. In addition to the use of the additives of the present invention in conventional carbon diesel fuels as above described, the additives also find utility with the newer generation of biodiesel fuels prepared from various vegetable type oils. Such biodiesel fuels are esters of naturally occurring fatty acids such as the product resulting from esterification of the tri-glycerides which form the predominance of the vegetable oils. In a particularly preferred practice of the invention wherein soybean oil is converted by conventional techniques to methyl soyate and glycerol, in accordance with the invention the glycerol is etherified by reaction with isobutylene or t-butanol or the corresponding C 5 materials, in order to produce a product mixture comprised primarily of the 1,2-di-t-alkyl glycerol, the 1,3-di-t-alkyl di-t-alkyl glycerol and the 1,2,3-tri-t-alkyl glycerol. Especially advantageous in this reaction is the use of a highly cross-linked sulfonic acid resin catalyst such as Amberlyst XN1010 with an isoalkene to glycerol ratio of 2:1 or higher at temperatures in the range of 50-150°C, preferably 55-75°C. Amberlyst is a trade name which may be registered as a trade made is one or more of the territories of this application. The product mixtures resulting from the reactions using this catalyst generally comprise 60 to 70% by weight 1,3-di-t-alkyl glycerol, 5 to 15 wt.% 1,2-di-t-alkyl glycerol and 15 to 30 wt.% 1,2,3-tri-t-alkyl glycerol. The glycerol ether product is soluble in all portions with the methyl soyate, and indeed it has been found that a blend of the glycerol ether with methyl soyate has certain special and unique utilities. For example, a blend of about 60 to 90 vol.% methyl soyate with 10 to 40% of the glycerol ether product mixture above described in turn forms an extremely satisfactory agent for blending with conventional hydrocarbon diesel fuels for purposes of reducing emissions. Generally, the soyate ether mixture is suitably blended in an amount of 1 to 30 vol.% with conventional low sulfur diesel fuels in order to provide a resulting fuel with enhanced emission reduction characteristics. An additional feature of the above described mixtures of the methyl soyate with the glycerol ether mixture is that the resulting mixture possesses unique solvent characteristics. In fact, the resulting mixture can be termed an environmentally friendly solvent and can be used to replace less friendly solvents in a wide number of solvent applications. We are aware of certain prior art which relates to etherification of glycerol using various acidic catalysts. Such are illustrated by U.S. Patent 1,968,033 and Czechoslovak 190,755. In each instance, the product mixture produced by such procedures does not appear to have the yield, composition or utility of the mixtures employed in accordance with the present invention. Product yields are low due to significant t-butyl alcohol formation. Monoethers, described in the references are highly water soluble and thus are totally unsuitable as diesel blending agents. There appears to be no reference in the procedures described in the said patents of the production of ether mixtures containing the 1,2,3 tri-alkyl ether as is a requirement in connection with the compositions of the present invention. EXAMPLE 1 -- DIESEL FUEL APPLICATIONS A. Fuel Solubility Fuel solubility is a primary requirement for diesel fuel applications. Not all oxygenates that are highly polar have good solubility in the new low aromatic reformulated diesel fuels. The solubility of a 70:10:20 1,3-di, 1,2-di, and 1,2,3-tri-t-butyl glycerol mixture by weight which is used in this and the following examples was determined in EPA 1991 certification diesel fuel which contained 400 ppm sulfur and 31% aromatics, and in 1993 CARB certification diesel fuel which contained 400 ppm sulfur and 10% aromatics. Results show the t-butyl glycerol mixture has infinite solubility. Experiments also show the t-butyl glycerol product mixture has infinite solubility in methyl soyate biodiesel fuels and in a wide variety of aliphatic hydrocarbons such as pentane and hexane. An 80:20 by volume mixture of methyl soyate and the above t-butyl glycerol mixture was prepared and blended at 30% with conventional EPA certification diesel fuel. Again, the methyl soyate/glycerol ether mixture is completely soluble in the diesel fuel. From all the above results, it can be concluded that the product mixture obtained from glycerol etherification with isobutylene will be completely miscible with the new generation of reformulated diesel fuels. B. Fuel Flashpoint The diesel fuel flashpoint with the oxygenate additive must be greater than 52.2°C (126°F) to use existing pipelines for distribution. Results show the flashpoint of a blend of 5% by volume of the above t-butyl glycerol mixture in EPA certification diesel fuel is 76.7°C (170°F). Results were also acceptable for 80:20 methyl soyate / t-butyl glycerol mixture blends at concentrations of 5-30% in EPA certification diesel fuels. From the above results, it can be concluded that diesel fuel blends prepared from conventional diesel fuels and containing the additives of the invention will have acceptable flashpoints and can be transferred through the normal pipeline distribution system. C. Water Partitioning Loss of diesel additives through water extraction is a significant environmental and performance issue. Both a high degree of water solubility in the fuel blend and high degree of water partitioning of the additive are undesirable. Additives that increase the water solubility in diesel above 0.05 wt.% are unacceptable. A 5 volume % blend of the t-butyl glycerol product mixture described above in EPA certification diesel fuel was prepared and evaluated for additive and water partitioning. The additive containing fuel was exposed to water at a 10:1 fuel/water ratio. After vigorous shaking, the layers were separated by centrifuging. The diesel fuel layer had a water concentration of 300 ppm's indicating very little water partitions into the diesel fuel phase. The t-butyl glycerol product mixture partition coefficient was calculated to be 0.1 indicating little t-butyl glycerol was removed from the diesel fuel phase into the aqueous phase. D. Cetane Number Some oxygenated diesel fuel additives can reduce the natural cetane number of the base diesel fuel. A 5 volume % blend of the di-t-butyl glycerol product mixture described above with EPA certification diesel fuel (31% aromatic content) was prepared and sent to an outside laboratory for cetane determination. Results are as follows: Fuel Type Cetane Number Reference Diesel Fuel 43 Oxygenated Diesel Fuel 44 No decrease in cetane number is observed when the di-t-butyl glycerol product mixture described above is blended with conventional diesel fuel. EXAMPLE 2 -- EMISSION TESTING Oxygenated diesel fuels prepared using the di-t-butyl glycerol product mixture above described with conventional EPA 1991 certification, 400 ppm sulfur, 31% aromatic, and 43 cetane diesel fuel are evaluated for emission reduction potential. The study was based on extrapolations from studies conducted using a prototype 1991 Detroit Diesel Series 60 heavy duty engine. Hot-start transient emissions are measured using the standard EPA transient test cycle. Diesel exhaust emissions, including: oxides of nitrogen (NO x ), carbon monoxide (CO), total hydrocarbons (HC), particulate matter (PM) and various non-regulated aldehyde and ketone emissions, benzene and particulate composition. The di-t-butyl glycerol product mixture above described in amounts of from 1 to 5% in EPA certification diesel is evaluated. The di-t-butyl glycerol product mixture combined with methyl soyate 20:80 is also blended at the 5 to 30% level with EPA certification diesel and evaluated for emission reduction potential. Both blends result in significant improvements in ability to reduce emissions. Both carbon monoxide, hydrocarbons, particulate matter, aldehyde/ketones and benzene are reduced by the additive addition. Although NO x emissions, in general, show small increases, the addition of chemical cetane improvers can be utilized to overcome and reduce the NO x emission increase. When the di-t-butyl glycerol mixture is added, the most significant emission reductions are observed for particulate matter. Particulate emission reduction results obtained by extrapolation from results achieved with comparable systems are as follows: Oxygen Additive Oxygen Content (wt.%) PM (G/B.HP-Hr.) EPA Base Fuel 0 0.182 MS (5%) 0.59 0.174 DTBG (1%) 0.56 0.169 DTBG (2%) 1.12 0.157 DTBG (5%) 2.80 0.135 MS/DTBG (5%) 1.03 0.151 MS/DTBG (10%) 2.06 0.144 MS=methyl soyate; DTBG=70:10:20 1,3-di, 1,2-di, and 1,2,3-tri-t-butyl glycerol; MS/DTBG=80:20 blend. EPA base reference fuel contained 31% aromatics, 400 ppm sulfur, and had a 43 natural cetane number.

Claims: A fuel composition comprised of hydrocarbons and/or vegetable oil derivatives boiling in the diesel fuel range and containing up to 500 ppm sulfur, and a particulate emission reducing amount of an additive comprising at least one glycerol ether having the formula wherein R 1 , and R 2 and R 3 are each hydrogen or a C 1 -C 10 alkyl group with the proviso that at least two of R 1 , R 2 or R 3 are C 1 -C 10 alkyl groups. A fuel composition as claimed in claim 1 which contains 0.1 to 15 vol.% of said additive. A fuel composition as claimed in claim 2 which contains 0.2 to 10 vol.% of said additive. A fuel composition as claimed in any one of claims 1 to 3 characterised in that R 1 and R 3 in the formula are tertiary alkyl groups having not more than 10 carbon atoms and R 2 is hydrogen. A fuel composition as claimed in any one of the preceding claims characterised in that R 1 and R 3 are C 4 -C 5 tertiary-alkyl groups. A fuel composition as claimed in any one of claims 1 to 3 characterised in that R 1 and R 2 and R 3 are C 4 -C 5 tertiary-alkyl groups. A fuel composition as claimed in any one of claims 1 to 3 characterised in that the additive comprises a mixture comprising a predominant amount of 1,3-di-t-alkyl glycerol and also comprising 1,2-di-t-alkyl glycerol and 1,2,3-tri-t-alkyl glycerol. A fuel composition as claimed in claim 7 characterised in that said mixture comprises by volume 60-70% 1,3-di-t-alkyl glycerol, 5-15% 1,2-di-t-alkyl glycerol and 15-30% 1,2,3-tri-t-alkyl glycerol and the alkyl groups are selected from C 4 -C 5 alkyl groups. A fuel composition as claimed in claim 9 characterised in that the alkyl group is C 4 . A fuel composition as claimed in claim 9 characterised in that the alkyl group is C 5 . A fuel composition as claimed in any one of the preceding claims characterised in that it comprises a blend of hydrocarbon diesel fuel and from 1 to 30 vol.% of a blend of 60 to 95 vol.% methyl soyate and 5 to 40 vol.% of a glycerol ether product mixture comprising primarily 1,3-di-t-alkyl glycerol, 1,2-di-t-alkyl glycerol and 1,2,3-tri-t-alkyl glycerol and the alkyl groups are selected from C 4 and C 5 alkyl groups. A fuel composition as claimed in any one of the preceding claims characterised in that it also contains a cetane improving amount of a peroxidic or nitrate cetane improver.

Inventors: KARAS LAWRENCE J, KESLING HAVEN S JR, LIOTTA FRANK J JR, KARAS, LAWRENCE J., KESLING JR., HAVEN S., LIOTTA JR., FRANK J.
Applicants: ARCO CHEM TECH, ARCO CHEMICAL TECHNOLOGY, L.P.
Application year: 1994
Main classification: C10L1
IPC codes: C10L1, C10L10, F02B3